WO2021170398A1 - Dishwash detergent product - Google Patents

Dishwash detergent product Download PDF

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Publication number
WO2021170398A1
WO2021170398A1 PCT/EP2021/053096 EP2021053096W WO2021170398A1 WO 2021170398 A1 WO2021170398 A1 WO 2021170398A1 EP 2021053096 W EP2021053096 W EP 2021053096W WO 2021170398 A1 WO2021170398 A1 WO 2021170398A1
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WO
WIPO (PCT)
Prior art keywords
detergent composition
machine
bleach
dishwasher
composition according
Prior art date
Application number
PCT/EP2021/053096
Other languages
English (en)
French (fr)
Inventor
Liam Edward DAVIES
Alexandre François BOUX DE CASSON
Robert John Carswell
Marina MIXTRO SERRASQUEIRO
Original Assignee
Unilever Ip Holdings B.V.
Unilever Global Ip Limited
Conopco, Inc., D/B/A Unilever
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever Ip Holdings B.V., Unilever Global Ip Limited, Conopco, Inc., D/B/A Unilever filed Critical Unilever Ip Holdings B.V.
Priority to US17/802,551 priority Critical patent/US20230140001A1/en
Priority to AU2021226049A priority patent/AU2021226049B2/en
Priority to EP21703934.6A priority patent/EP4110892A1/de
Priority to CN202180017008.7A priority patent/CN115151629A/zh
Publication of WO2021170398A1 publication Critical patent/WO2021170398A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to a machine dishwash detergent product which provides good cleaning at low wash temperatures and which is suitable to comply with the technical Ecolabel criteria as specified in the EU Commission Decision 2017/1216.
  • Machine dishwash detergent products typically contain several different active components, including builders, surfactants, enzymes and bleaching agents.
  • Surfactants are employed to remove stains and soil and to disperse the released components into the cleaning liquid.
  • Enzymes help to remove stubborn stains of proteins, starch and lipids by hydrolyzing these components.
  • Bleach is used to remove stains by oxidizing the components that make up these stains.
  • 'builders' complexing agents
  • the EU Ecolabel criteria sets-out technical criteria a machine dishwash detergent product must meet in order for a manufacturer to be allowed to apply the Ecolabel certification mark onto their products.
  • the criteria sets-out strong limitations on the type and amounts of many ingredients. For example it sets upper limits of the amount of total non-biodegradable detergent actives as well as outright excluding the presence of others. Examples of not-readily biodegradable detergent actives can be found in the ‘Detergent ingredient database’ list (DID list) available on the EU Ecolabel website (https://ec.europa.eu/environment/archives/ecolabel/pdf/did_list/didlist_part_a_en.pdf).
  • DID list Detergent ingredient database
  • MnOx (a-Manganese (II) oxalate dihydrate) is a known bleach catalyst which is not toxic to aquatic life and hence is suitable to be included at normal levels in machine dishwash detergents designed to meet the EU Ecolabel technical criteria.
  • MnOx bleach catalyst at commonly applied concentrations did not provide adequate bleaching in a tested formulation which meets the EU Ecolabel criteria.
  • a unit dose or non-unit dose machine dishwash detergent composition comprising: ⁇ bleach;
  • the invention also relates to a process of washing dishware in a machine dishwasher, comprising the following steps: a) placing dishware into a machine dishwasher; b) adding a detergent composition to the machine dishwasher in an amount of from 5 to 50 grams; c) running the machine dishwasher, which includes bringing into contact the dishware with a wash liquor formed by mixing the detergent composition with water; d) removing the wash liquor and optionally drying the dishware; wherein the detergent composition added at step b) comprises:
  • the total detergent composition added at step b) comprises, if present, at most 1 gram, and if in non-unit dose form at most 14.3 wt.%, in total of the following ingredients:
  • the invention further relates to use of a bleach catalyst according for enhancing cleaning in detergent compositions according to the invention and meet the technical criteria as set out in the EU Commission Decision 2017/1216 ‘establishing the EU Ecolabel criteria for dishwasher detergents’. Detailed description of the invention
  • Weight percentage is based on the total weight of the detergent composition unless otherwise indicated or as made clear from the context. It will be appreciated that the total weight amount of ingredients will not exceed 100 wt. %. Whenever an amount or concentration of a component is quantified herein, unless indicated otherwise, the quantified amount or quantified concentration relates to said component per se, even though it may be common practice to add such a component in the form of a solution or of a blend with one or more other ingredients. It is furthermore to be understood that the verb "to comprise” and its conjugations is used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded.
  • the indefinite article “a” or “an” does not exclude the possibility that more than one of the elements is present, unless the context clearly requires that there be one and only one of the elements.
  • the indefinite article “a” or “an” thus usually means “at least one”. Unless otherwise specified all measurements are taken at standard conditions. Whenever a parameter, such as a concentration or a ratio, is said to be less than a certain upper limit it should be understood that in the absence of a specified lower limit the lower limit for said parameter is 0.
  • the term “the composition is free of” or “free of” means that the composition comprises less than 0.1 wt.%, by weight of the total composition, of the specified component(s).
  • the term “the composition is free of” of “free of” means that the composition comprises less than 0.01 wt.%, by weight of the total composition, of the specified component(s), more preferably less than 0.001 wt.% of the specified component(s) and most preferably less than 0.0001 wt.% of the specified component(s).
  • the term “the composition is free of” means that the composition comprises less than 0.1 wt.%, more preferably less than 0.01 wt.% of phosphates; alkyl phenol ethoxylates; atranol; chloroatranol; Diethylenetriaminepentaacetic acid (DTPA); Ethylenediaminetetraacetic acid (EDTA) and its salts; glutaraldehyde; microplastics; nitromusks and polycyclic musks; perfluorinated alkylates; reactive chlorine compounds; rhodamine B; sodium hydroxyl methyl glycinate; triclosan; 3-iodo-2-propynyl butylcarbamate Bleach
  • composition of the invention preferably comprises from 1 to 25 wt. %, more preferably from 5 to 20 wt. % and even more preferably from 8 to 15 wt. % of bleach.
  • Inorganic and/or organic bleaches can be used.
  • Bleach may be selected from peroxides, organic peracids, salts of organic peracids and combinations thereof.
  • peroxides are acids and corresponding salts of monopersulphate, perborate monohydrate, perborate tetrahydrate, and percarbonate.
  • Organic peracids useful herein include alkyl peroxy acids and aryl peroxyacids such as peroxybenzoic acid and ring- substituted peroxybenzoic acids (e.g. peroxy-alpha-naphthoic acid), aliphatic and substituted aliphatic monoperoxy acids (e.g. peroxylauric acid and peroxystearic acid), and phthaloyl amido peroxy caproic acid (PAP).
  • peroxybenzoic acid and ring- substituted peroxybenzoic acids e.g. peroxy-alpha-naphthoic acid
  • aliphatic and substituted aliphatic monoperoxy acids e.g. peroxylauric acid and peroxystearic acid
  • PAP phthaloyl amido peroxy caproic acid
  • Typical diperoxy acids useful herein include alkyl diperoxy acids and aryldiperoxy acids, such as 1,12-di-peroxy- dodecanedioic acid (DPDA), 1,9-diperoxyazelaic acid, diperoxybrassylic acid, diperoxysebacic acid and diperoxy-isophthalic acid, and 2-decyldiperoxybutane-1, 4- dioic acid.
  • DPDA 1,12-di-peroxy- dodecanedioic acid
  • 1,9-diperoxyazelaic acid diperoxybrassylic acid
  • diperoxysebacic acid and diperoxy-isophthalic acid diperoxy-isophthalic acid
  • 2-decyldiperoxybutane-1, 4- dioic acid 2-decyldiperoxybutane-1, 4- dioic acid.
  • the bleach of the present composition is selected from peroxides (including peroxide salts such as sodium percarbonate), organic peracids, salts of organic peracids and combinations thereof. More preferably, the bleach is a peroxide. Most preferably, the bleach is a percarbonate. Further preferred, the bleach is a coated percarbonate.
  • the detergent composition may contain one or more bleach activators such as peroxyacid bleach precursors.
  • Peroxyacid bleach precursors are well known in the art. As non-limiting examples can be named N, N, N', N'-tetraacetyl ethylene diamine (TAED), sodium nonanoyloxybenzene sulphonate (SNOBS), sodium benzoyloxybenzene sul phonate (SBOBS) and the cationic peroxyacid precursor (SPCC) as described in US-A-4, 751, 015.
  • the detergent composition of the invention preferably comprises from 0.01 to 15 wt. % of bleach activator, more preferably from 0.2 to 10 wt. % and even more preferably from 1.0 to 6 wt. %.
  • Bleach catalyst such as peroxyacid bleach precursors.
  • peroxyacid bleach precursors are well known in the art. As non-limiting examples can be named N, N, N', N'-tetraacetyl ethylene diamine
  • Bleach catalysts function by oxidizing typically via peroxide or a peracid to form a bleaching species. They require the presence of an oxidizable soil so that they can be reduced back to the starting bleach activator state.
  • the bleach catalyst according used in the invention is a manganese complex of formula (A):
  • Such bleach catalysts are described in EP0458397A2.
  • the preferred features of the manganese-based bleach catalyst described therein are preferred as well for the purposes of this invention and explicitly belong to the description of this invention.
  • the preferred features referred to are described on pages 3 to 8 of EP0458397A2 in sofar as relating to manganese-based bleach catalysts.
  • the bleach catalysts of the invention are preferably one or more of: • [Mn m Mn lv (m-O)i (m-OA (Me-TACN) 2 ] (PF 6 ) 2 ;
  • the still even more preferred bleach catalyst is Mn lv 2 (p-0) 3 (Me-TACN) 2 ] (PFe) 2 .
  • the amount of the bleach catalyst is from 0.001 to below 0.010 wt. %, as based on actives levels.
  • the preferred form of adding the bleach catalyst is as of part of a bleach catalyst granule comprising less than 5 wt. % of active bleach catalyst. The use of such granules improves the accurate dosing of the bleach catalyst.
  • the preferred level of the bleach catalyst (i.e. as active) according to the invention is from 0.002 to 0.01 wt. %, preferably from 0.003 to 0.01 wt. %, more preferably from 0.005 to 0.009 wt. %, even more preferred from 0.007 to 0.009 wt. %.
  • the detergent composition may comprise further bleach catalyst of a type not according to the invention, but this is not preferred.
  • the bleach catalyst is preferably physically separated from the bleach in the detergent composition to prevent premature bleaching.
  • Preferred ways of separating are by incorporation into different solid parts of the detergent composition (e.g. different layers of a tablet) and/or by into different compartments of a multi-compartmental capsule and/or by addition of the bleach catalyst as an encapsulate.
  • the detergent product of the invention comprises 0.1 to 30 wt. % of surfactant, more preferably 0.5 to 25 wt. % and even more preferably 1.5 to 15 wt. %.
  • the surfactant can be non-ionic or anionic or a mixture thereof.
  • nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents” Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon’s Emulsifiers and Detergents” published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981.
  • the surfactants used are saturated.
  • the composition contains from 0.1 to 15 wt. %, more preferably from 0.5 to 10 wt. % and most preferably from 1 to 5 wt. % of a nonionic surfactant or a mixture of two or more non-ionic surfactants.
  • a nonionic surfactant or a mixture of two or more non-ionic surfactants.
  • a combination of at least two nonionic surfactants is used.
  • functional groups include hydroxy, carboxy, mercapto, amino or amido groups.
  • Examples of useful hydrophobes of commercial nonionic surfactants include C8- C18 alkyl fatty alcohols, C8-C14 alkyl phenols, C8-C18 alkyl fatty acids, C8-C18 alkyl mercaptans, C8-C18 alkyl fatty amines, C8-C18 alkyl amides and C8-C18 alkyl fatty alkanolamides.
  • suitable ethoxylated fatty alcohols may be chosen from ethoxylated cetyl alcohol, ethoxylated ketostearyl alcohol, ethoxylated isotridecyl alcohol, ethoxylated lauric alcohol, ethoxylated oleyl alcohol and mixtures thereof.
  • suitable nonionic surfactants for use in the invention are found in the low- to non-foaming ethoxylated/ propoxylated straight-chain alcohols of the PlurafacTM LF series, supplied by the BASF and the SynperonicTM NCA series supplied by Croda.
  • end-capped ethoxylated alcohols available as the SLF 18 series from BASF and the alkylpolyethylene glycol ethers made from a linear, saturated C16-C18 fatty alcohol of the LutensolTM AT series, supplied by BASF.
  • suitable nonionics to apply in the composition of the invention are modified fatty alcohol polyglycolethers available as DehyponTM E127, DehyponTM 3697 GRA or DehyponTM Wet from BASF/Cognis.
  • nonionics from the LutensolTM TO series of BASF which are alkylpolyethylene glycol ethers made from a saturated iso-C13 alcohol.
  • Amineoxide surfactants may also be used in the present invention as anti-redeposition surfactant.
  • suitable amineoxide surfactants are C10-C18 alkyl dimethylamine oxide and C10-C18 acylamido alkyl dimethylamine oxide.
  • the total amount present preferably is less than 5 wt. %, and more preferably not more than 2 wt. %. Furthermore, if an anionic surfactant is present, it is preferred that an antifoam agent to suppress foaming is present.
  • suitable anionic surfactants are methylester sulphonates or sodium lauryl sulphate.
  • the builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
  • Water used to provide a wash liquor in the dishwasher usually contains calcium, magnesium, and metallic cations (iron, copper, and manganese).
  • Builders remove the hard water ions typically through precipitation, chelation, or ion exchange. In addition, they help remove soil by dispersion.
  • a beneficial amount of builder is from 10 to 80 wt. %, more preferably from 20 to 75 wt. %, even more preferably from 30 to 70 wt. % and still even more preferably from 40 to 65 wt. %.
  • Examples of precipitating builder materials include sodium carbonate.
  • Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070. Zeolite and carbonate (carbonate (including bicarbonate and sesquicarbonate) are preferred builders, whereof carbonate is the more preferred.
  • the composition may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate. This is typically present at a level of less than 15 wt. %.
  • Aluminosilicates are materials having the general formula:
  • the preferred sodium aluminosilicates contain 1.5-3.5 S1O2 units in the formula above. They can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. The ratio of surfactants to alumuminosilicate (where present) is preferably greater than 5:2, more preferably greater than 3:1.
  • Aminopolycarboxylates are well known in the detergent industry and sometimes referred to as aminocarboxylate chelants. They are generally appreciated as being strong builders. Examples include glutamic acid N,N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA), ethylenediaminedisuccinic acid (EDDS), iminodisuccinic acid (IDS), iminodimalic acid (IDM), nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), hydroxyethyliminodiacetic acid (HEIDA) aspartic acid diethoxysuccinic acid (AES) aspartic acid-N,N-diacetic acid (ASDA) , hydroxyethylene- diaminetetraacetic acid (HEDTA), hydroxyethylethylene-diaminetriacetic acid (HEEDTA) , iminodifumaric (IDF), iminoditartaric acid (IDT), imin
  • Preferred aminopolycarboxylate builders are GLDA, MGDA and/or EDDS, of which GLDA and MGDA are the more preferred, and MGDA is even more preferred.
  • the builder of the detergent composition comprises a builder selected from at least one of a) aminopolycarboxylate, b) citric acid and/or its alkalimetal salt and and c) carbonate.
  • the builder preferably comprises builders from a) and b); a) and c) or a) and c); and more preferably comprises builders from a), b) and c).
  • the detergent composition comprises:
  • the detergent composition of the invention comprises enzymes which degrade, alter or facilitate the degradation or alteration of biochemical soils and stains encountered in cleansing situations so as to remove more easily the soil or stain from the object being washed to make the soil or stain more removable in a subsequent cleansing step. Both degradation and alteration can improve soil removal.
  • enzymes suitable for use in the cleaning compositions of this invention include lipases, cellulases, peroxidases, proteases (proteolytic enzymes), amylases (amylolytic enzymes) and others.
  • proteases proteases
  • amylases amylases
  • Other enzymes are proteases, amylases, cellulases, peroxidases, mannanases, pectate lyases and lipases and combinations thereof.
  • the enzymes most commonly used in detergent compositions are proteolytic and amylolytic enzymes.
  • Enzymes may be added in liquid or in encapsulated form. In a preferred embodiment of this invention the enzymes are present in encapsulated form.
  • Well know enzyme stabilizers such as polyalcohols/borax, calcium, formate or protease inhibitors like 4-formylphenyl boronic acid may also be present in the composition
  • the proteolytic enzymes in this invention include metalloproteases and serine proteases, including neutral or alkaline microbial serine protease, such as subtilisins (EC 3.4.21.62).
  • the proteolytic enzymes for use in the present invention can be those derived from bacteria of fungi. Chemically or genetically modified mutants (variants) are included.
  • Preferred proteolytic enzymes are those derived from Bacillus, such as B. lentus, B. gibsonii, B. subtilis, B. licheniformis, B. alkalophilus, B. amyloliquefaciens and Bacillus pumilus, of which B. lentus and B. gibsonii are most preferred.
  • proteolytic enzymes examples include ExcellaseTM,ProperaseTM, PurafectTM, PurafectTM Prime, PurafectTMOx by Genencor; and those sold under the trade names BlazeTM, OvozymeTM, SavinaseTM, AlcalaseTM, EverlaseTM, EsperaseTM, RelaseTM, PolarzymeTM, LiquinaseTMand CoronaseTM by Novozymes.
  • Preferred levels of protease are from 0.1 to 10 mg, more preferably from 0.2 to 5 mg, most preferably 0.4 to about 4 mg active protease per gram of the detergent composition.
  • amylolytic enzymes for use in the present invention can be those derived from bacteria or fungi. Chemically or genetically modified mutants (variants) are included.
  • Preferred amylolytic enzyme is an alpha-amylase derived from a strain of Bacillus, such as B. subtilis, B. licheniformis, B. amyloliquefaciens or B. stearothermophilus. Examples of such amylolytic enzymes are produced and distributed under the trade name of StainzymeTM, StainzymeTM Plus, TermamylTM, NatalaseTM and DuramylTM by Novozymes; as well as PoweraseTM, PurastarTM, PurastarTM Oxam by Genencor.
  • StainzymeTM, StainzymeTM Plus and PoweraseTM are the preferred amylases.
  • Preferred levels of amylase are from 0.01 to 5, more preferably from 0.02 to 2, most preferably from 0.05 to about 1 mg active amylase per gram of the detergent composition.
  • the enzymes may suitably be incorporated in the detergent composition in liquid or in encapsulated form. In case the composition has a pH of 9.0 and more it is preferred to employ enzymes in encapsulated form. Examples of encapsulated forms are enzyme granule types D, E and HS by Genencor and granule types, T, GT, TXT and EvityTM of Novozymes.
  • the composition contains active protease and the protease activity of the freshly prepared composition decreases by not more than 70%, more preferably by not more than 50% and most preferably by not more than 20% when the composition is stored in a closed container for 8 weeks at 20 degrees Celsius.
  • the detergent composition comprises a combination of amylase and protease.
  • the detergent composition comprises at least one dispersing polymer.
  • Dispersing polymers as are beneficially chosen from the group of anti-spotting agents and/or anti-scaling agents.
  • suitable anti spotting polymeric agents include hydrophobically modified polycarboxylic acids such as AcusolTM460 ND (ex Dow) and AlcosperseTM747 by Nouryon, whereas also synthetic clays, and preferably those synthetic clays which have a high surface area are very useful to prevent spots, in particular those formed where soil and dispersed remnants are present at places where the water collects on the glass and spots formed when the water subsequently evaporates.
  • Suitable anti-scaling agents are water soluble dispersing polymers prepared from an allyloxybenzenesulfonic acid monomer, a methallyl sulfonic acid monomer, a copolymerizable nonionic monomer and a copolymerizable olefinically unsaturated carboxylic acid monomer as described in US5547612 or known as acrylic sulphonated polymers as described in EP851022.
  • Polymers of this type include polyacrylate with methyl methacrylate, sodium methallyl sulphonate and sulphophenol methallyl ether such as AlcosperseTM240 supplied (Nouryon).
  • terpolymer containing polyacrylate with 2-acrylamido-2 methylpropane sulphonic acid such as Acumer 3100 supplied by Dow.
  • polymers and co-polymers of acrylic acid having a molecular weight between 500 and 20,000 can also be used, such as homo-polymeric polycarboxyl ic acid compounds with acrylic acid as the monomeric unit.
  • the average weight of such homo-polymers in the acid form preferably ranges from 1,000 to 100,000 particularly from 3,000 to 10,000 e.g. Sokolan TM PA 25 from BASF or AcusolTM425 from Dow.
  • polycarboxylates co-polymers derived from monomers of acrylic acid and maleic acid such as CP5 from BASF.
  • the average molecular weight of these polymers in the acid form preferably ranges from 4,000 to 70,000.
  • Modified polycarboxylates like SokalanTM CP50 from BASF or AlcoguardTM4160 from Nouryon may also be used.
  • Mixture of anti-scaling agents may also be used. Particularly useful is a mixture of organic phosphonates and polymers of acrylic acid. It is preferable if the level of dispersing polymers ranges from 0.2 to 6 wt. % of the total composition, preferably from 0.5 to 5 wt. %, and further preferred from 1 to 4 wt. %.
  • Suitable anti-scaling agents include organic phosphonates, amino carboxylates, polyfunctionally-substituted compounds, and mixtures thereof. Particularly preferred anti-scaling agents are organic phosphonates such as a-hydroxy-2 phenyl ethyl diphosphonate, ethylene diphosphonate, hydroxy 1,1-hexylidene, vinylidene 1,1- diphosphonate, 1,2-dihydroxyethane 1,1- diphosphonate and hydroxy-ethylene 1,1- diphosphonate. Most preferred is hydroxy-ethylene 1,1- diphosphonate (EDHP) and 2- phosphono-butane, 1,2,4-tricarboxylic acid (Bayhibit ex Bayer).
  • the detergent composition beneficially comprises from 0.5 to 5 wt. % of EDHP, more preferably from 1 to 4 wt. % and even more preferably from 1.5 to 3.0 wt. %
  • the combined amount of EDHP plus acrylic acid based dispersant polymer preferably is from 1 to 6 wt. %, more preferably from 2 to 5 wt. %.
  • Glass corrosion inhibitors can prevent the irreversible corrosion and iridescence of glass surfaces in machine dishwash detergents.
  • the claimed composition may suitably contain glass corrosion inhibitors.
  • Suitable glass corrosion agents can be selected from the group the group consisting of salts of zinc, bismuth, aluminum, tin, magnesium, calcium, strontium, titanium, zirconium, manganese, lanthanum, mixtures thereof and precursors thereof. Most preferred are salts of bismuth, magnesium or zinc or combinations thereof.
  • Usual preferred levels of glass corrosion inhibitors in the present composition are 0.01- 2 wt. %, more preferably 0.01- 0.5 wt. %.
  • Anti-tarnishing agents may prevent or reduce the tarnishing, corrosion or oxidation of metals such as silver, copper, aluminum and stainless steel.
  • Anti-tarnishing agents such as benzotriazole or bisbenzotriazole and substituted or substituted derivatives thereof and those described in EP723577 (Unilever) may also be included in the composition.
  • Other anti-tarnishing agents that may be included in the detergent composition are mentioned in WO 94/26860 and WO 94/26859.
  • Suitable redox active agents are for example complexes chosen from the group of cerium, cobalt, hafnium, gallium, manganese, titanium, vanadium, zinc or zirconium, in which the metal are in the oxidation state of II, II, IV V or VI. In view of reducing the environmental impact of the detergent composition of the invention the detergent composition is free of zinc and bismuth.
  • the present composition may suitably contain a non-surfactant, water-soluble, liquid binder, e.g. in a concentration of 0-50% by weight of the continuous phase.
  • liquid binders include polyethylene glycols, polypropylene glycols, glycerol, glycerol carbonate, ethylene glycol, propylene gylcol and propylene carbonate.
  • polyethylene glycols with a molecular weight of at most 4000 preferred are polyethylene glycols with a molecular weight of at most 4000.
  • the advantageous amount of polyethylene glycols with a molecular weight of at most 4000 is below 5 wt. % more preferably below 3 wt. %, below 2 wt. %, below 1 wt. % and in fact most beneficially the detergent composition is free of polyethylene glycols.
  • the detergent product of the invention comprises one or more colorants, perfumes or a mixture thereof in an amount of from 0.0001 to 8 wt. %, more preferably from 0.001 to 4 wt. % and even more preferably from 0.001 to 1.5 wt. %.
  • Perfume is preferably present in the range from 0.1 to 1 wt. %.
  • CTFA Cosmetic, Toiletry and Fragrance Association
  • perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co. In perfume mixtures preferably 15 to 25 wt. % are top notes.
  • Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]).
  • Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.
  • the detergent composition of the invention restricts the total amount of a number of not- readily biodegradable ingredients to be at most 14.3 wt. % preferably at most 12 wt.%, more preferably at most 10 wt.%, even more preferably at most 7 wt.%, if the present at all.
  • These ingredients are useful actives in the field of machine dish wash:
  • phosphonates discussed above as anti-scalling agent
  • ⁇ polyethylene glycols with a molecular weight of greater than 4000 discussed above as binder
  • PVP polyvinylpyrrolidon
  • PVPO poly(vinylpyridine-N-oxide)
  • PVPVI polyvinylpyrrolidone-vinylimidazole
  • the preferred process of washing dishware in a machine dishwasher using the detergent composition according to the invention is to add a dosage amount of detergent composition which provides at most 1 gram per dose of the combined weight of these not-readily biodegradable compounds.
  • the form of the detergent product is in unit-dose form (e.g. a multi- compartmental capsule or a tablet) than the total amount of these not-readily biodegradable ingredients is at most 1 gram, preferably at most 0.8, more preferably at most 0.7 gram, even more preferably at most 0.5 gram per unit dose.
  • the concentration of such not-readily biodegradable ingredients is preferably at most 12.0 wt. %, 10.0 wt. %, 7.0 wt. %, 5.0 wt. %, 3.0 wt. %, 2.0 wt. % and even more preferably at most 1.0 wt. %.
  • the amount of: ⁇ 2-methyl-2H-isothiazol-3-one (MIT) preferably is at preferably at most 0,0050 wt. %;
  • • 1 ,2-Benzisothiazol-3(2H)-one (BIT) is preferably at most 0,0050 wt. %
  • the detergent composition is preferably free of all the following ingredients: • phosphates;
  • Ethylenediaminetetraacetic acid EDTA and its salts
  • Microplastics i.e. insoluble macromolecular plastics with a maximum length of below 5mm, not intentionally added, but may be present as impurity; ⁇ nitromusks;
  • the detergent product of the invention may be in any suitable form.
  • the detergent product is preferably provided as a water-soluble or water-dispersible unit dose.
  • Particularly preferred unit doses are in the form of pouches, which comprise at least one further non-shape stable ingredient, such as a liquid and/or powder; or in the form of tablets.
  • the unit dose is sized and shaped as to fit in the detergent cup of a conventional house-hold machine dishwasher as is known in the art.
  • the unit-dose detergent product has a unit weight of 5 to 50 grams, more preferably a unit weight of 10 to 30 grams, even more preferably a unit weight of 12 to 25 grams and even more beneficially from 15 to 20 grams.
  • Advantageous unit dose pouches have more than one compartment.
  • Advantageous unit dose tablets are those which have more than one visually distinct tablet region. Such regions can be formed by e.g. two distinct (colored) layers or a tablet having a main body and a distinct insert, such as forming a nested egg.
  • one benefit of using multi-compartmental pouches/ multi-region tablets is that it can be used to reduce/prevent undesired chemical reactions between two or more ingredients during storage by physical segregation.
  • the more preferred unit dose form is a tablet, in particular a multi-layer tablet and even more preferably a multi-layer tablet comprising at least one white part and at least one colored part.
  • the unit dose detergent product is wrapped to improve hygiene and consumer safety.
  • the wrapper advantageously is based on water-soluble film which preferably a polyvinylalcohol (PVA) based film.
  • PVA polyvinylalcohol
  • the dishwasher composition is a wrapped unit dose.
  • Such wrapping prevents direct contact of the detergent product with the skin of the consumer when placing the unit dose in the detergent cup/holder of a e.g. machine dishwasher.
  • a further benefit of course is that the consumer also does not need to remove a water-soluble wrapping before use.
  • the detergent composition is suitably contained in a package.
  • the package is based on paper (e.g. cardboard).
  • the package is preferably in the form of a (plastic) bottle with an internal volume of from 100 to 2000 ml and preferably of from 400 to 1600 ml.
  • the package i.e. the primary container which holds the detergent product, such as the plurality of unit doses
  • the package preferably contains an outwardly visible logo of the EU Ecolabel.
  • the package preferably contains one or more of the following technical information, which are of course, if present, preferably outwardly visible:
  • the detergent products according to the invention can be made using known methods and equipment in the field of detergent product manufacturing.
  • the invention also relates to a process of washing dishware in a machine dishwasher, comprising the following steps: a) placing dishware into a machine dishwasher; b) adding a detergent composition to the machine dishwasher in an amount of from 5 to 50 grams; c) running the machine dishwasher, which includes bringing into contact the dishware with a wash liquor formed by mixing the detergent composition with water; d) removing the wash liquor and optionally drying the dishware; wherein the detergent composition added at step b) comprises:
  • CMI carboxymethyl inulin
  • HM-CMC hydrophobically modified CMC
  • silicone silicone
  • PVP polyvinylpyrrolidon
  • PVVI poly(vinylimidazole)
  • PVPO poly(vinylpyridine-N-oxide)
  • PVVI polyvinylpyr
  • the preferred amount of detergent composition added at step b) (e.g. in the dishwasher detergent cup) is from 7 to 30 grams, more preferably from 10 to 25 grams and even more preferably from 12 to 20 grams.
  • the machine dish washing process is a domestic machine dish washing process.
  • the invention further relates to use of a bleach catalyst according to the invention for enhancing cleaning in detergent compositions which meet the technical criteria as set out in the EU Commission Decision 2017/1216 ‘establishing the EU Ecolabel criteria for dishwasher detergents’.
  • Example 1
  • Powder detergent formulations were made as set out in Table 1 : Table 1 - powder detergent formulations (wt. % actives):
  • Example 1 cleaning scores were significantly improved versus that using the detergent powder according to Comparative B (and Comparative A). The cleaning scores of Comparative A did not differ significantly from that of Comparative B.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Catalysts (AREA)
PCT/EP2021/053096 2020-02-28 2021-02-09 Dishwash detergent product WO2021170398A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US17/802,551 US20230140001A1 (en) 2020-02-28 2021-02-09 Dishwash detergent product
AU2021226049A AU2021226049B2 (en) 2020-02-28 2021-02-09 Dishwash detergent product
EP21703934.6A EP4110892A1 (de) 2020-02-28 2021-02-09 Geschirrspülmittelprodukt
CN202180017008.7A CN115151629A (zh) 2020-02-28 2021-02-09 餐具洗涤剂产品

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EP20160173.9 2020-02-28
EP20160173 2020-02-28

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US (1) US20230140001A1 (de)
EP (1) EP4110892A1 (de)
CN (1) CN115151629A (de)
AU (1) AU2021226049B2 (de)
WO (1) WO2021170398A1 (de)

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DE102022206583A1 (de) 2022-06-29 2024-01-04 Henkel Ag & Co. Kgaa Reinigungsmittel

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EP0458397A2 (de) 1990-05-21 1991-11-27 Unilever N.V. Bleichmittelaktivierung
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EP0723577A1 (de) 1993-10-14 1996-07-31 Unilever N.V. Waschmittelzusammensetzungen enthaltend mittel zur verhinderung des anlaufens von silber
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Publication number Priority date Publication date Assignee Title
DE102022206583A1 (de) 2022-06-29 2024-01-04 Henkel Ag & Co. Kgaa Reinigungsmittel

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US20230140001A1 (en) 2023-05-04
AU2021226049A1 (en) 2022-09-15
EP4110892A1 (de) 2023-01-04
CN115151629A (zh) 2022-10-04

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